| 1. |
- Kel, Oksana, et al.
(author)
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Chiral Selectivity in the Binding of [4]Helicene Derivatives to Double-Stranded DNA
- 2013
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In: Chemistry - A European Journal. - : Wiley. - 1521-3765 .- 0947-6539. ; 19:22, s. 7173-7180
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Journal article (peer-reviewed)abstract
- The interaction of a series of chiral cationic [4]helicene derivatives, which differ by their substituents, with double-stranded DNA has been investigated by using a combination of spectroscopic techniques, including time-resolved fluorescence, fluorescence anisotropy, and linear dichroism. Addition of DNA to helicene solutions results to a hypochromic shift of the visible absorption bands, an increase of fluorescence quantum yield and lifetime, a slowing down of fluorescence anisotropy decay, and a linear dichroism in flow-oriented DNA, which unambiguously points to the binding of these dyes to DNA. Both helicene monomers and dimeric aggregates, which form at higher concentration, bind to DNA, the former most probably upon intercalation and the latter upon groove binding. The binding constant depends substantially on the dye substituents and is, in all cases, larger with the M than the P enantiomer, by factors ranging from 1.2 to 2.3, depending on the dye.
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| 2. |
- Quanz, Sascha P., et al.
(author)
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Atmospheric characterization of terrestrial exoplanets in the mid-infrared : biosignatures, habitability, and diversity
- 2022
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In: Experimental astronomy. - : Springer Science and Business Media LLC. - 0922-6435 .- 1572-9508. ; 54:2-3, s. 1197-1221
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Journal article (peer-reviewed)abstract
- Exoplanet science is one of the most thriving fields of modern astrophysics. A major goal is the atmospheric characterization of dozens of small, terrestrial exoplanets in order to search for signatures in their atmospheres that indicate biological activity, assess their ability to provide conditions for life as we know it, and investigate their expected atmospheric diversity. None of the currently adopted projects or missions, from ground or in space, can address these goals. In this White Paper, submitted to ESA in response to the Voyage 2050 Call, we argue that a large space-based mission designed to detect and investigate thermal emission spectra of terrestrial exoplanets in the mid-infrared wavelength range provides unique scientific potential to address these goals and surpasses the capabilities of other approaches. While NASA might be focusing on large missions that aim to detect terrestrial planets in reflected light, ESA has the opportunity to take leadership and spearhead the development of a large mid-infrared exoplanet mission within the scope of the “Voyage 2050” long-term plan establishing Europe at the forefront of exoplanet science for decades to come. Given the ambitious science goals of such a mission, additional international partners might be interested in participating and contributing to a roadmap that, in the long run, leads to a successful implementation. A new, dedicated development program funded by ESA to help reduce development and implementation cost and further push some of the required key technologies would be a first important step in this direction. Ultimately, a large mid-infrared exoplanet imaging mission will be needed to help answer one of humankind’s most fundamental questions: “How unique is our Earth?”
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| 3. |
- Zalubovskis, Raivis, et al.
(author)
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Self-adaptable Catalysts : Substrate-Dependent Ligand Configuration
- 2008
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In: Journal of the American Chemical Society. - Washington DC : American Chemical Society. - 0002-7863 .- 1520-5126. ; 130:6, s. 1845-1855
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Journal article (peer-reviewed)abstract
- Pd(II) allyl and Pd(0) olefin complexes containing the configurationally labile ligand 1,2-bis-[4,5dihydro-3H-dibenzo[c-e]azepino]ethane were studied as models for intermediates in Pd-catalyzed allylic alkylations. According to NMR and DFT studies, the ligand prefers C-s conformation in both eta(3)-1,3-diphenylpropenyl and eta(3)-cyclohexenyl Pd(II) complexes, whereas in Pd(0) olefin complexes it adopts different conformations in complexes derived from the two types of allyl systems in both solution and, as verified by X-ray crystallography, in the solid state. These results demonstrate that the Pd complex is capable of adapting its structure to the reacting substrate. The different structural preferences also provide an explanation for the behavior of 1,3-diphenyl-2-propenyl acetate and 2-cyclohexenyl acetate in Pd-catalyzed allylic alkylations using pseudo-C-2 and pseudo-C-s symmetric ligands.
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